First- and second-order phase transitions in the adlayer of biadipate on Au(111)

The adsorption of biadipate on Au(111) was studied by cyclic voltammetry and chronocoulometry. The biadipate adlayer undergoes a potential-driven phase transition. It is shown that the phase transition can be either of the first- or second-order depending on the biadipate concentration. At low surfactant concentrations, the first-order transition is characterised by a discontinuity in the charge density-potential curve and by the presence of very sharp peaks in the voltammetric response. At higher concentrations, these peaks are no longer observed but a discontinuity in the capacity curve is still noticeable, in agreement with a second-order transition. © the Owner Societies.

Second-Order Training of Adaptive Critics for Online Process Control

A new algorithm for training of nonlinear optimal neuro-controllers (in the form of the model-free, action-dependent, adaptive critic paradigm). Overcomes problems with existing stochastic backpropagation training: need for data storage, parameter shadowing and poor convergence, offering significant benefits for online applications.

Second-order distorted wave calculation for electron impact ionization of hydrogen

The triple differential cross sections for ionization of atomic hydrogen by electron impact are analysed in the case of coplanar, asymmetric geometry within the framework of second- order distorted wave theory. Detailed calculations are performed without making any approximations (other than numerical) in the evaluation of the second-order amplitude. The present results are compared with experimental measurements and other theoretical calculations for incident energies of 250, 150 and 54.4 eV. It is found that the second-order calculations represent a marked improvement over the results obtained from first-order theories for impact energies of 150 eV and higher. The close agreement between the present second-order plane wave calculation and those of Byron et al calculated using the closure approximation at an incident energy of 250 eV implies that the closure approximation is valid for this energy. The large difference between the present second-order distorted wave calculations and experiment at an incident energy of 54.4 eV suggests that higher order effects are important for incident energies less than 100 eV.

Hybridization of a class of "second order" models of traffic flow

Despite the simultaneous progress of traffic modelling both on the macroscopic and microscopic front, recent works [E. Bourrel, J.B. Lessort, Mixing micro and macro representation of traffic flow: a hybrid model based on the LWR theory, Transport. Res. Rec. 1852 (2003) 193–200; D. Helbing, M. Treiber, Critical discussion of “synchronized flow”, Coop. Transport. Dyn. 1 (2002) 2.1–2.24; A. Hennecke, M. Treiber, D. Helbing, Macroscopic simulations of open systems and micro–macro link, in: D. Helbing, H.J. Herrmann, M. Schreckenberg, D.E. Wolf (Eds.), Traffic and Granular Flow ’99, Springer, Berlin, 2000, pp. 383–388] highlighted that one of the most promising way to simulate efficiently traffic flow on large road networks is a clever combination of both traffic representations: the hybrid modelling. Our focus in this paper is to propose two hybrid models for which the macroscopic (resp. mesoscopic) part is based on a class of second order model [A. Aw, M. Rascle, Resurection of second order models of traffic flow?, SIAM J. Appl. Math. 60 (2000) 916–938] whereas the microscopic part is a Follow-the Leader type model [D.C. Gazis, R. Herman, R.W. Rothery, Nonlinear follow-the-leader models of traffic flow, Oper. Res. 9 (1961) 545–567; R. Herman, I. Prigogine, Kinetic Theory of Vehicular Traffic, American Elsevier, New York, 1971]. For the first hybrid model, we define precisely the translation of boundary conditions at interfaces and for the second one we explain the synchronization processes. Furthermore, through some numerical simulations we show that the waves propagation is not disturbed and the mass is accurately conserved when passing from one traffic representation to another.

Getting off the escalator? A study of Scots out-migration from a global city region

Something new is happening to reverse the historical trend of skilled Scots moving to London for career progression. The Scottish population of London and the South East is falling and this despite Scots enjoying continued occupational success within the South East labour market. The authors ask why Scots are leaving the UK's main escalator region and then investigate how these migration changes can best be theorised relative to literature on the mobility of the 'new service class'. Building on Fielding's escalator region hypothesis, the authors report on recent research on longer distance flows out of the UK's main escalator region. They advance the critique of the escalator region hypothesis set out by Findlay et al and ask why people would leave a global city offering good opportunities for occupational mobility. Demographic regime change provides only a partial answer. Other explanations can be found in the changing mobilities of the new service class as they engage in what Smith has defined as 'translocal' and 'transnational' urbanism. The authors argue that Scotland's changing relationship with London and the South East may be representative of a wider set of changes in migration linkages between regional economies and global cities.

Second-order NMR spectra at high field of common organic functional groups

The proton NMR spectra of aryl n-propyl sulfides gave rise to what may appear to be first-order proton NMR spectra. Upon oxidation to the corresponding sulfone, the spectra changed appearance dramatically and were clearly second-order. A detailed analysis of these second-order spectra, in the sulfone series, provided vicinal coupling constants which indicated that these compounds had a moderate preference for the anti-conformer, reflecting the much greater size of the sulfone over the sulfide. It also emerged, from this study, that the criterion for observing large second-order effects in the proton NMR spectra of 1,2-disubstituted ethanes was that the difference in vicinal coupling constants must be large and the difference in geminal coupling constants must be small. n-Propyl triphenylphosphonium bromide and 2-trimethylsilylethanesulfonyl chloride, and derivatives thereof, also exhibited second-order spectra, again due to the bulky substituents. Since these spectra are second-order due to magnetic nonequivalence of the nuclei in question, not chemical shifts, the proton spectra are perpetually second-order and can never be rendered first-order by using higher field NMR spectrometers.

Modelling road traffic accidents using macroscopic second-order models of traffic flow

In this paper, we introduce a macroscopic model for road traffic accidents along highway sections. We discuss the motivation and the derivation of such a model, and we present its mathematical properties. The results are presented by means of examples where a section of a crowded one-way highway contains in the middle a cluster of drivers whose dynamics are prone to road traffic accidents. We discuss the coupling conditions and present some existence results of weak solutions to the associated Riemann Problems. Furthermore, we illustrate some features of the proposed model through some numerical simulations. © The authors 2012.